The present invention relates to solder alloys which are completely free from lead and yet suitable for use in soldering of electronic devices without producing thermal damage.
Sn-Pb alloys have been used in soldering since ancient times, and they are still most popular for soldering electronic devices to printed circuit boards or other substrates.
When they are to be discarded, electronic appliances including televisions, radios, audio or video recorders, computers, copying or printing machines, etc. may be disposed of in landfills, since they are composed of various materials such as synthetic resins used for housings and printed circuit boards, and metals used for wires and other electric connections, and frames, and are not suitable for disposal by incineration.
In recent years, the phenomenon of acid rain has become serious since the acidity of rain is increasing mainly due to discharge of sulfur oxide into the atmosphere by extensive use of fossil fuels such as gasolines and fuel (heavy) oils. Acid rain causes the solders used in discarded electronic appliances present in landfills to dissolve and penetrate into the ground. If such contaminated groundwater is ingested by a person for many years, the accumulation of lead in the person""s body may result in lead poisoning (plumbism). From this viewpoint, there is a need of a lead-free solder alloy in the electronics industry.
Conventional lead-free solder alloys are Sn-based alloys such as Sn-Ag and Sn-Sb alloys. In Sn-Ag alloys, an Sn-3.5Ag alloy is the eutectic composition with a melting temperature of 221xc2x0 C. Even if this composition having the lowest melting temperature among Sn-Ag alloys is used as a solder alloy, the soldering temperature will be as high as from 260xc2x0 C. to 280xc2x0 C., which may cause thermal damage to heat-sensitive electronic devices during soldering, thereby deteriorating their functions or rupturing the devices. Of Sn-Sb alloys, an Sn-5Sb alloy has the lowest melting temperature, but its melting temperature is as high as 235xc2x0 C. in the solidus line and 240xc2x0 C. in the liquidus line. Therefore, the soldering temperature is in the range of from 280xc2x0 C. to 300xc2x0 C., which is still higher than that of the Sn-3.5Ag alloy, and thermal damage to heat-sensitive electronic devices cannot be avoided.
In view of the relatively high melting temperatures of Sn-Ag and Sn-Sb alloys as solder alloys, many attempts to lower their melting temperatures have been proposed. See, for example, Japanese Patent Applications Laid-Open (JP A1) Nos. 6-15476(1994), 6-344180(1994), 7-1178(1995), 7-40079(1995), and 7-51883(1995).
The solder alloys disclosed in these Japanese patent applications contain Bi and/or In (indium) in a large proportion in order to lower the melting temperatures. Although Bi and In are both effective for decreasing the melting temperatures of Sn-Ag and Sn-Sb solder alloys, the addition of Bi and/or In in a large amount is accompanied by the following problems. Addition of Bi in a large proportion makes the solder alloys very hard and brittle. As a result, it is impossible or difficult to subject the solder alloys to plastic working into wire, or when they are used to solder electronic devices, the soldered joints may be readily detached when subjected to only a slight impact. Addition of indium in a large proportion to solder alloys is undesirable due to its very high cost.
In order to avoid thermal damage to electronic devices during soldering, the soldering temperature should be 250xc2x0 C. or lower, and in order to perform soldering at such a temperature, it is desirable that the liquidus temperature of the solder alloy be 210xc2x0 C. or lower and preferably 200xc2x0 C. or lower.
However, with the above-described approaches to lower the melting temperatures of Sn-Ag and Sn-Sb solder alloys by addition of Bi and/or In, it is difficult to decrease the liquidus temperature of the alloys to 200xc2x0 C. or lower unless Bi and/or In is added in a large amount. Furthermore, even though it is possible to provide a solder alloy having a liquidus temperature lowered to 200xc2x0 C. or lower by such a means, the solidus temperature thereof, at which solidification of the alloy is completed, may also be lowered even more, so that it takes a prolonged period of time to completely solidify the solder alloy in soldered joints formed by soldering. As a result, if the soldered joints is subjected to any vibration or impact before they are completely solidified, they may be cracked.
Another problem of conventional lead-free solder alloys is that those lead-free alloys having liquidus temperatures which are low enough to be close to their solidus temperatures do not have satisfactory mechanical properties such as tensile strength and elongation, thereby forming soldered joints which have poor bonding strength or which are liable to be detached upon impact.
It is an object of the present invention to provide lead-free solder alloys having a liquidus temperature which is below 210xc2x0 C. and preferably below 200xc2x0 C. and a solidus temperature or peak temperature, at which solidification of the alloy is completed or substantially completed, is relatively close to the liquidus temperature.
It is another object of the present invention to provide lead-free solder alloys which have good bonding strength when used for soldering.
A more specific object of the present invention is to provide a lead-free solder alloy having the following properties.
1) It can be used at a soldering temperature below 250xc2x0 C. and preferably from 230xc2x0 C. to 240xc2x0 C. so as to prevent thermal damage to heat-sensitive electronic devices during soldering.
2) It has quite good solderability.
3) It has a narrow (solidification) temperature range between the liquidus and solidus temperatures (or peak temperate at which solidification is substantially completed) such that the alloy is rapidly solidified after soldering in order to prevent the resulting soldered joints from being cracked when vibration or an impact is applied immediately after soldering, the temperature range being close to the eutectic temperature of Sn-Pb alloy.
4) It produces soldered joints having a bonding strength which is high enough to prevent the joints from being detached upon application of an impact.
5) It can be easily subjected to plastic working into wire such that it can be used for soldering with a solder iron.
An Sn-based alloy having a eutectic temperature close to that of an Sn-Pb eutectic alloy (183xc2x0 C.) is an Sn-9Zn alloy (eutectic temperature: 199xc2x0 C.). However, the mechanical strength, particularly the tensile strength of the Sn-9Zn alloy is not so high that it cannot form soldered joints having good bonding strength. We have found that addition of Ni, Ag, and/or Cu is quite effective in order to improve the tensile strength and hence bonding strength of Sn-Zn alloys to such a degree that they can be adequately used to solder electronic devices.
The melting temperatures of the resulting alloys having improved tensile strength may be increased to such a degree that electronic devices may be thermally damaged during soldering, particularly when Ag is added. In such cases, addition of Bi in a relatively large amount along with Ag results in improvement in the tensile strength of Sn-Zn alloys without a significant increase in the melting temperatures.
The present invention provides a lead-free solder alloy consisting essentially of:
(1) A lead-free solder alloy consisting essentially of:
from 7 to 10 wt % of Zn,
at least one of from 0.01 to 1 wt % of Ni, from 0.1 to 3.5 wt % of Ag, and from 0.1 to 3 wt % of Cu,
from 0 to 6 wt % of Bi,
from 0 to 3 wt % of In,
from 0 to 1 wt % of P, and
a balance of Sn.
(2) The lead-free solder alloy of (1) which contains at least one of from 0.2 to 6 wt % of Bi and from 0.5 to 3 wt % of In.
(3) A lead-free solder alloy of (1) which consists essentially of:
from 7 to 10 wt % of Zn,
at least one of from 0.1 to 3.5 wt % of Ag, and from 0.1 to 3 wt % of Cu,
from 0 to 6 wt % of Bi,
from 0 to 3 wt % of In,
from 0 to 1 wt % of P, and
a balance of Sn.
(4) The lead-free solder alloy of (3) which contains at least one of from 0.2 to 6 wt % of Bi and from 0.5 to 3 wt % of In.
(5) The lead-free solder alloy of (1) which has a tensile strength of at least 5 kgf/mm2 and at least 10% elongation.
(6) The lead-free solder alloy of (1) which has a liquidus temperature of 210xc2x0 C. or lower and a solidus temperature of 180xc2x0 C. or higher.
(7) A lead-free solder alloy consisting essentially of:
from 2 to 10 wt % of Zn,
from 10 to 30 wt % of Bi,
from 0.05 to 2 wt % of Ag,
from 0 to 1 wt % of P, and
a balance of Sn.
(8) The lead-free solder alloy of (7) which has a tensile strength of at least 10 kgf/mm2 and at least 10% elongation.
(9) The lead-free solder alloy of (7) which has a liquidus temperature of 200xc2x0 C. or lower and a peak temperature of 170xc2x0 C. or higher.
(10) The lead-free solder alloy of one of from (1) to (9) which contains from 0.001 to 1 wt % of P.
(11) A lead-free solder alloy consisting essentially of:
from 2 to 10 wt % of Zn,
from 0.01 to 1 wt % of Ni,
from 0.2 to 30 wt % of Bi, and
a balance of Sn,
said solder alloy having a tensile strength of at least 5 kgf/mm2 and an elongation of at least 10%.
(12) A lead-free solder alloy consisting essentially of:
from 2 to 10 wt % of Zn,
from 0.1 to 3 wt % of Cu,
from 0.2 to 30 wt % of Bi, and
a balance of Sn,
said solder alloy having a tensile strength of at least 5 kgf/mm2 and an elongation of at least 10%.
(13) A lead-free solder alloy consisting essentially of:
from 2 to 10 wt % of Zn,
from 0.01 to 1 wt % of Ni,
from 0.1 to 3 wt % of Cu,
from 0.2 to 30 wt % of Bi, and
a balance of Sn,
said solder alloy having a tensile strength of at least 5 kgf/mm2 and an elongation of at least 10%.
(14) The lead-free solder alloy of one of from (11) to (13) which contains from 7 to 10 wt % of Zn.
(15) The lead-free solder alloy of (14) which contains from 0.001 to 1 wt % of P.